CA2491048A1 - Process for the preparation of block copolymers - Google Patents
Process for the preparation of block copolymers Download PDFInfo
- Publication number
- CA2491048A1 CA2491048A1 CA002491048A CA2491048A CA2491048A1 CA 2491048 A1 CA2491048 A1 CA 2491048A1 CA 002491048 A CA002491048 A CA 002491048A CA 2491048 A CA2491048 A CA 2491048A CA 2491048 A1 CA2491048 A1 CA 2491048A1
- Authority
- CA
- Canada
- Prior art keywords
- process according
- isoindole
- dihydro
- polymerization
- general formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Graft Or Block Polymers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
- Polymerization Catalysts (AREA)
- Materials For Medical Uses (AREA)
Abstract
Process for the preparation of block copolymers, based on vinylaromatic monomers and monomers deriving from (meth)acrylic acid by means of radicalic polymerization which comprises polymerizing the monomers at a temperature higher than or equal to 120~C, in the presence of a radicalic initiating system comprising a compound having general Formula (I).
Claims (12)
1. process for the preparation of block copolymers by means of radicalic polymerization which comprises:
a) polymerizing a vinylaromatic monomer at a temperature higher than or equal to 120°C in the presence of a radi-calic initiating system comprising a compound having general formula (I):
wherein R1 and R2, the same or different, represent a methyl or ethyl radical, X1 represents a hydrogen atom, X2 represents a hydrogen atom or a hydroxyl or X1 and X2, the same or different, represent a C1-C4 (iso)alkyl radical, or, they jointly form an aromatic ring, n is equal to zero or 1 and R3 represents a radical selected from one of the following groups:
-C(CH3)2-CN;
-C(CH3)2-Ph;
-CHCH3Ph;
or R3 is absent, as in that position there is an un-coupled electron.
until a conversion of the monomer ranging from 5 to 99.9% is obtained;
b) feeding to the polymerization mixture of step (a), after obtaining the desired conversion, a monomer deriving from (meth)acrylic acid in such a quantity that, at the end of the polymerization, the total weight of the block copolymer Mw is lower than 1,000,000, operating at the same temperature and in the presence of the same initi-ating system;
c) recovering, at the end of the polymerization, the block copolymer thus obtained.
a) polymerizing a vinylaromatic monomer at a temperature higher than or equal to 120°C in the presence of a radi-calic initiating system comprising a compound having general formula (I):
wherein R1 and R2, the same or different, represent a methyl or ethyl radical, X1 represents a hydrogen atom, X2 represents a hydrogen atom or a hydroxyl or X1 and X2, the same or different, represent a C1-C4 (iso)alkyl radical, or, they jointly form an aromatic ring, n is equal to zero or 1 and R3 represents a radical selected from one of the following groups:
-C(CH3)2-CN;
-C(CH3)2-Ph;
-CHCH3Ph;
or R3 is absent, as in that position there is an un-coupled electron.
until a conversion of the monomer ranging from 5 to 99.9% is obtained;
b) feeding to the polymerization mixture of step (a), after obtaining the desired conversion, a monomer deriving from (meth)acrylic acid in such a quantity that, at the end of the polymerization, the total weight of the block copolymer Mw is lower than 1,000,000, operating at the same temperature and in the presence of the same initi-ating system;
c) recovering, at the end of the polymerization, the block copolymer thus obtained.
2. The process according to claim 1, wherein the R3 group is -C(CH3)2-CN.
3. The process according to claim 1, wherein the R3 group is -C(CH3)2-Ph.
4. The process according to claim 1, wherein the R3 group is -CHCH3Ph.
5. The process according to claim 1, wherein the R3 group is absent.
6. The process according to any of the previous claims, wherein the polymerization of both step (a) and step (b) is carried out at a temperature ranging from 120 to 150°C.
7. The process according to any of the previous claims, wherein the initiator having general formula (I) is present in concentrations ranging from 0.01 to 2% in moles with re-spect to the total moles of the monomers fed.
radical generator compounds (G) selected from peroxides, peresters, percarbonates, azobisdial-kyldinitriles, with molar ratios I/G lower than 4;
radical generator compounds (G) selected from peroxides, peresters, percarbonates, azobisdial-kyldinitriles, with molar ratios I/G lower than 4;
8. The process according to claim 1, wherein the initia-tor having general formula (I) is used with free radical generators (G) selected from dibenzoyl peroxide, dicumyl peroxide, N,N'-azobis-(diisobutyronitrile) with molar ra-tios I/G ranging from 1 to 3.
9. The process according to any of the previous claims, wherein the polymerization of both steps (a) and (b) is carried out batchwise, in continuous or semi-continuous at a temperature higher than 120°C and at a pressure which is such as to maintain the monomers in liquid phase.
10. The process according to any of the previous claims, wherein in the radicalic initiating system having general formula (I), X1 and X2 jointly form an aromatic ring, and n is equal to zero.
11. The process according to claim 10, wherein the initia-tor having general formula (I) is selected from:
1,1,3,3-tetraethyl-2-(2-cyanoprop-2-yl)-2,3-dihydro-1H-isoindole;
1,1,3,3-tetraethyl-2-(2-phenylprop-2-yl)-2,3-dihydro-1H-isoindole;
1,1,3,3-tetraethyl-2-(2-phenylethyl)-2,3-dihydro-1H-isoindole;
1,1,3,3-tetramethyl-2-(2-cyanoprop-2-yl)-2,3-dihydro-1H-isoindole;
1,1,3,3-tetramethyl-2-(2-phenylprop-2-yl)-2,3-dihydro-1H-isoindole:
1,1,3,3-tetramethyl-2-(2-phenylethyl)-2,3-dihydro-1H-isoindole.
1,1,3,3-tetraethyl-2-(2-cyanoprop-2-yl)-2,3-dihydro-1H-isoindole;
1,1,3,3-tetraethyl-2-(2-phenylprop-2-yl)-2,3-dihydro-1H-isoindole;
1,1,3,3-tetraethyl-2-(2-phenylethyl)-2,3-dihydro-1H-isoindole;
1,1,3,3-tetramethyl-2-(2-cyanoprop-2-yl)-2,3-dihydro-1H-isoindole;
1,1,3,3-tetramethyl-2-(2-phenylprop-2-yl)-2,3-dihydro-1H-isoindole:
1,1,3,3-tetramethyl-2-(2-phenylethyl)-2,3-dihydro-1H-isoindole.
12. Block copolymers based on vinylaromatic monomers and monomers deriving from (meth)acrylic acid obtained with the process according to any of the previous claims.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT001495A ITMI20021495A1 (en) | 2002-07-09 | 2002-07-09 | PROCEDURE FOR THE PREPARATION OF BLOCK COPOLYMERS. |
| ITMI2002A001495 | 2002-07-09 | ||
| PCT/EP2003/006837 WO2004005361A1 (en) | 2002-07-09 | 2003-06-26 | Process for the preparation of block copolymers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2491048A1 true CA2491048A1 (en) | 2004-01-15 |
| CA2491048C CA2491048C (en) | 2010-08-31 |
Family
ID=30012500
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2491048A Expired - Fee Related CA2491048C (en) | 2002-07-09 | 2003-06-26 | Process for the preparation of block copolymers |
Country Status (15)
| Country | Link |
|---|---|
| US (1) | US7388052B2 (en) |
| EP (1) | EP1519970B1 (en) |
| JP (1) | JP4477493B2 (en) |
| CN (1) | CN1308363C (en) |
| AT (1) | ATE376562T1 (en) |
| AU (1) | AU2003242772A1 (en) |
| BR (1) | BR0312348B1 (en) |
| CA (1) | CA2491048C (en) |
| DE (1) | DE60317066T2 (en) |
| ES (1) | ES2295643T3 (en) |
| IT (1) | ITMI20021495A1 (en) |
| MX (1) | MXPA04012791A (en) |
| PL (1) | PL209004B1 (en) |
| RU (1) | RU2320675C2 (en) |
| WO (1) | WO2004005361A1 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ITMI20040752A1 (en) * | 2004-04-16 | 2004-07-16 | Polimeri Europa Spa | PROCEDURE FOR THE PREPARATION OF VINYLAROMATIC CO POLYMERS SEAMED ON ELASTOMETER IN A CONTROLLED WAY |
| US8344058B2 (en) * | 2005-08-26 | 2013-01-01 | CID Centro de Investigación y Desarrollo Technológico S.A. de C.V. | Reactive block copolymers as additives for the preparation of silicate-polymer composites |
| US8357759B2 (en) | 2005-08-26 | 2013-01-22 | CID Centro de Investigación y Desarrollo Tecnológico S.A. de C.V. | Reactive block copolymers |
| US8557907B2 (en) * | 2005-08-26 | 2013-10-15 | Macro-M S.A. De C.V. | Reactive block copolymers for the preparation of inorganic tubule-polymer composites |
| US20100311920A1 (en) * | 2005-08-26 | 2010-12-09 | Cid Centro De Investigacion Y Desarrollo Tecnologico Sa De Cv | Using Reactive Block Copolymers as Chain Extenders and Surface Modifiers |
| US20100311849A1 (en) | 2006-08-23 | 2010-12-09 | Cid Centro De Investigacion Y Desarrollo Tecnologico Sa De Cv | Using Reactive Block Copolymers as Chain Extenders and Surface Modifiers |
| JP5229167B2 (en) * | 2009-09-04 | 2013-07-03 | 株式会社リコー | Composition for radical polymerization and method for producing polymer |
| ITMI20121973A1 (en) | 2012-11-20 | 2014-05-21 | Versalis Spa | SELF-EXTINGUISHING POLYMER COMPOSITION |
| FR3008986B1 (en) * | 2013-07-25 | 2016-12-30 | Arkema France | METHOD OF CONTROLLING THE PERIOD CHARACTERIZING THE MORPHOLOGY OBTAINED FROM A MIXTURE OF BLOCK COPOLYMER AND (CO) POLYMER FROM ONE OF THE BLOCKS |
| BR112016020481A2 (en) * | 2014-03-07 | 2018-06-05 | Basf Se | Process for polymerization of a vinyl monomer, first polymer, block polymer, composition, and compound |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997027233A1 (en) * | 1996-01-25 | 1997-07-31 | Basf Aktiengesellschaft | Block copolymers |
| US6281311B1 (en) | 1997-03-31 | 2001-08-28 | Pmd Holdings Corp. | Controlled free radical polymerization process |
| US6111025A (en) * | 1997-06-24 | 2000-08-29 | The Lubrizol Corporation | Block copolymer surfactants prepared by stabilized free-radical polymerization |
| FR2781487B1 (en) * | 1998-07-10 | 2000-12-08 | Atochem Elf Sa | EMULSION POLYMERIZATION IN THE PRESENCE OF A STABLE FREE RADICAL |
| CA2316785A1 (en) | 1998-10-26 | 2000-05-04 | The Lubrizol Corporation | Radial polymers prepared by stabilized free radical polymerization |
| US20020010267A1 (en) * | 1999-03-09 | 2002-01-24 | Symyx Technologies, Inc., A Delaware Corporation | Block copolymers |
| US6569162B2 (en) * | 2001-03-29 | 2003-05-27 | Ding Sheng He | Passively self-cooled electrode design for ablation catheters |
| TW574236B (en) * | 2000-09-25 | 2004-02-01 | Ciba Sc Holding Ag | Process for controlled radical polymerization in aqueous dispersion |
-
2002
- 2002-07-09 IT IT001495A patent/ITMI20021495A1/en unknown
-
2003
- 2003-06-26 AT AT03762534T patent/ATE376562T1/en not_active IP Right Cessation
- 2003-06-26 ES ES03762534T patent/ES2295643T3/en not_active Expired - Lifetime
- 2003-06-26 CA CA2491048A patent/CA2491048C/en not_active Expired - Fee Related
- 2003-06-26 RU RU2004138077/04A patent/RU2320675C2/en active
- 2003-06-26 AU AU2003242772A patent/AU2003242772A1/en not_active Abandoned
- 2003-06-26 US US10/518,550 patent/US7388052B2/en active Active
- 2003-06-26 PL PL373261A patent/PL209004B1/en unknown
- 2003-06-26 CN CNB038160951A patent/CN1308363C/en not_active Expired - Fee Related
- 2003-06-26 WO PCT/EP2003/006837 patent/WO2004005361A1/en active IP Right Grant
- 2003-06-26 MX MXPA04012791A patent/MXPA04012791A/en active IP Right Grant
- 2003-06-26 EP EP03762534A patent/EP1519970B1/en not_active Expired - Lifetime
- 2003-06-26 DE DE60317066T patent/DE60317066T2/en not_active Expired - Lifetime
- 2003-06-26 BR BRPI0312348-0A patent/BR0312348B1/en not_active IP Right Cessation
- 2003-06-26 JP JP2004518602A patent/JP4477493B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| EP1519970B1 (en) | 2007-10-24 |
| RU2320675C2 (en) | 2008-03-27 |
| CN1665855A (en) | 2005-09-07 |
| ATE376562T1 (en) | 2007-11-15 |
| US7388052B2 (en) | 2008-06-17 |
| CN1308363C (en) | 2007-04-04 |
| JP4477493B2 (en) | 2010-06-09 |
| BR0312348A (en) | 2005-04-05 |
| MXPA04012791A (en) | 2005-02-24 |
| DE60317066T2 (en) | 2008-08-07 |
| ITMI20021495A1 (en) | 2002-10-08 |
| BR0312348B1 (en) | 2012-12-25 |
| US20070219329A1 (en) | 2007-09-20 |
| DE60317066D1 (en) | 2007-12-06 |
| JP2005532442A (en) | 2005-10-27 |
| ES2295643T3 (en) | 2008-04-16 |
| PL373261A1 (en) | 2005-08-22 |
| AU2003242772A1 (en) | 2004-01-23 |
| RU2004138077A (en) | 2005-08-20 |
| PL209004B1 (en) | 2011-07-29 |
| EP1519970A1 (en) | 2005-04-06 |
| WO2004005361A1 (en) | 2004-01-15 |
| CA2491048C (en) | 2010-08-31 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |
Effective date: 20210628 |